USOO5914-101A

United States Patent (19) 11 Patent Number: 5,914,101

Tapley et al. (45) Date of Patent: Jun. 22, 1999
54 ZINCOXIDE DISPERSIONS 5,573,753 11/1996 Tapley.
FOREIGN PATENT DOCUMENTS
75 Inventors: Carole Allyson Maria Tapley,
Stockton on Tees; Philip Laurence O 595 471 5/1994 European Pat. Off..
Lyth, Middlesbrough; Iain Michael 2-212414 8/1990 Japan .
Harper, Redcar, all of United Kingdom 3-18362O 8/1991 Japan .
1503 28O 3/1978 United Kingdom.
73 Assignee: Tioxide Specialties Limited, London, 2 184356 6/1987 United Kingdom.
United Kingdom 2 207 426 2/1989 United Kingdom.
2 207434 2/1989 United Kingdom.
2 278 055 11/1994 United Kingdom.
21 Appl. No.: 08/907,201 90/O6974 6/1990 WIPO.
92/13517 8/1992 WIPO.
22 Filed: Aug. 6, 1997 WO 93/22386 11/1993 WIPO.
30 Foreign Application Priority Data OTHER PUBLICATIONS
Aug. 13, 1996 GB United Kingdom ................... 96.16978 Database WPI, Section Ch, Week 9522, Derwent Publica
51) Int. Cl. ................................ A61K 7/42; A61K 7/00 tions Ltd., London, GB; Class A60, AN 95-167072,
52 U.S. C. ... ... 424/59; 106/425; 106/426; XP002048129 & JP 07 089 710 A (Nippon Color Kogyo
106/428; 106/436; 252/313.1; 423/99: 424/60; KK), Apr. 4, 21995.
424/400; 424/401 Primary Examiner. Shelley A. Dodson
58 Field of Search ................................ 424/89, 60, 400, 57 ABSTRACT
424/401; 106/423, 436; 252/313.1; 423/436
56) References Cited A Stabilised aqueous dispersion of particulate Zinc oxide
comprises water, a Stabilising agent and Zinc oxide, the
U.S. PATENT DOCUMENTS particles of which are coated with dense amorphous Silica.
Useful Stabilising agents include cellulose ethers which
2,885,366 5/1959 Iler. contain quaternary ammonium groups and polyalkylene
3,472,840 10/1969 Stone et al. ............................. 424/401 glycols. The dispersions have excellent Stability at high
3,576,656 4/1971 Webb et al..
4,923,518 5/1990 Brand et al.. concentrations of Zinc oxide and are useful for preparing
5,068,056 11/1991 Robb. Sunscreen formulations, cosmetics and veterinary products.
5,366,660 11/1994 Tapley.
5,516,457 5/1996 Dahms. 28 Claims, No Drawings
 5,914,101
1 2
ZNC OXDE DISPERSIONS
This invention relates to dispersions of Zinc oxide and
particularly to aqueous dispersions of coated particles of
Zinc oxide.
Zinc oxide in a dispersed form is used in a number of
formulations which contain water. Such formulations
include Sunscreening preparations, cosmetics and Veterinary
products. The preparation of these formulations is greatly
eased if the Zinc oxide is available in the form of an aqueous
dispersion which can be readily incorporated into the for
mulation. However, Stable dispersions of Zinc oxide are
difficult to prepare and the Zinc oxide may dissolve at low or
high pH values.
It is an object of this invention to provide a stable
aqueous dispersion of Zinc oxide which can be used to
prepare Such formulations.
According to the invention, a Stabilised aqueous disper
Sion of particulate Zinc oxide comprises water, a Stabilising
agent and Zinc oxide, the particles of which are coated with
dense amorphous Silica which has been deposited on the
Surface of the Zinc oxide particles by mixing an alkali metal
Silicate and an acid in the presence of Zinc oxide particles in
an aqueous Suspension, the aqueous Suspension being main
tained at a pH of at least 8 during the mixing of Said Silicate
and Said acid.
The particle Size of the Zinc oxide is chosen to Suit the
final use for the dispersed particles. A particularly preferred
Stabilised dispersion according to the invention is useful in
forming Sunscreen preparations and, in this dispersion, the
average primary particle Size of the Zinc oxide is in the range
0.005 to 0.20 micrometre. Preferably, the average primary
particle size is in the range 0.01 to 0.10 micrometre and,
more preferably, in the range 0.03 to 0.07 micrometre. The
Zinc oxide particles useful for SunScreen preparations pref
erably are Substantially equiaxial and the average primary
particle size is determined by measuring the average diam
eter of unagglomerated particles. According to this
invention, the particles are provided with a coating.
However, the preferred dimensions refer to the uncoated
particles.
The Stabilised dispersions of the invention are particu
larly useful when they contain a relatively high proportion of
Zinc oxide since this allows a user to have flexibility in
producing the formulations in which the dispersions are
used. Useful Stabilised dispersions contain at least 40 per
cent Zinc oxide by weight and preferably the amount of Zinc
oxide is at least 50 per cent by weight. Particularly useful
Stabilised dispersions contain at least 60 per cent Zinc oxide
by weight. Normally, it is impractical to prepare a dispersion
containing more than 75 per cent Zinc oxide by weight.
Dense amorphous Silica is a form of Silica which is well
known, particularly in the art of inorganic pigments, as a
coating agent for particles. The dense Silica is Substantially
non-porous and amorphous and generally forms a continu
ous coating over the particles of Zinc oxide. It is character
ised by the method by which it is formed, namely the dense
Silica is precipitated at alkaline Suspension of Zinc oxide
having a pH of at least 8, and, preferably, a pH of from 9 to
11. In preparing the dispersions according to the invention
precipitation takes place in the presence of Zinc oxide
particles. The dense Silica is deposited by mixing an acid
Such as hydrochloric acid or Sulphuric acid and an alkaline
Solution of an alkali metal Silicate in the presence of Zinc
oxide to convert the Silicate to dense amorphous Silica. For
instance, a Solution of a Soluble alkali metal Silicate can be
mixed with an alkaline Suspension of the particles of Zinc
oxide to be coated and the resulting mixture is slowly
acidified to deposit dense amorphous Silica. Alternatively,
there can be added to a Suspension of the particles of Zinc
oxide an alkaline Solution of an alkali metal Silicate and,
Simultaneously, a mineral acid, to maintain the pH of the
Suspension at a value of at least 8, Say 9 to 11, to form and
deposit the required dense amorphous Silica coating. Once
the Silica has been fully deposited, the pH of the Suspension
is normally adjusted by further addition of acid to a value in
the range 6 to 8.
Generally the temperature of the Suspension is main
tained at a value of at least 60° C. and, possibly, up to 100
C., preferably from 70° C. to 90° C. during deposition of
dense amorphous Silica and the Suspension will be Stirred to
15 maintain effective coating.
Any Suitable alkali metal Silicate can be used as the
Source of dense amorphous Silica. Particularly useful are
Sodium and potassium Silicates and preferably, also, the
Solution of the Silicate is freshly prepared.
Normally, a dispersing agent is added to the Zinc oxide
Suspension to ensure that the Zinc oxide remains well
distributed in the Suspension during coating. A very conve
nient dispersing agent is an alkali metal Silicate Such as
Sodium or potassium Silicate. This dispersing agent will
25 usually become deposited as dense amorphous Silica during
the coating process. When added, the amount of Silicate used
as a dispersing agent is preferably in the range 1.0 to 5.0
weight per cent expressed as SiO2 with respect to Zinc oxide.
Sufficient dense amorphous Silica is usually deposited
upon the particles to form a complete layer over the indi
vidual particles. When the Zinc oxide has an average primary
particle size in the range 0.005 to 0.20 micrometre, the
preferred amount of dense amorphous silica deposited is in
the range 5 to 20 per cent by weight calculated as SiO2 with
35 respect to Zinc oxide. Preferably, for this particle size, the
amount of dense amorphous Silica is in the range 7 to 12 per
cent by weight as SiO2 with respect to Zinc oxide.
In addition to the coating of dense amorphous Silica
coatings of other hydrous oxides Such as oxides of
40 aluminium, Zirconium or titanium may also be present on the
Zinc oxide particles. Although these deposited hydrous
oxides are generally described as being present in the form
of a coating, this does not necessarily imply that the Zinc
oxide particles are completely or uniformly covered with
45 these hydrous oxides. The hydrous oxide can be deposited
by any Suitable means Such as by hydrolysis of a Soluble
compound of the appropriate metal in the presence of a Zinc
oxide Suspension.
Usually, after coating with dense amorphous Silica and,
50 if applicable, any other oxide, the Zinc oxide particles are
Separated by filtration, for example, and dried.
In one embodiment of the invention, the Stabilising agent
used in the dispersion is a cellulose ether which contains
quaternary ammonium groups. Particularly Suitable Stabilis
55 ing agents are those polymers described in U.S. Pat. No.
3,472,840 which are polymers having a backbone of anhy
droglucose units with pendant Substituent groups containing
quaternary ammonium functionality Spaced along this back
bone. Preferably, additional ether groups which do not
60 contain a quaternary ammonium radical will also be present
in the molecule. Such additional ether groups include alkyl,
hydroxyalkyl, alkoxyalkyl and hydroxyalkoxyalkyl ether
groups. The quaternary ammonium groups are preferably
derived from a quaternary epoxide or a quaternary halohy
65 drin. Particularly preferred Stabilising agents are quaternary
ammonium chlorides of hydroxyethyl cellulose reacted with
a trimethyl ammonium Substituted epoxide. Such products
 5,914,101
3 4
have been allocated the INCI Name Polyduaternium-10.
Stabilising agents covered by this description and useful in
this invention include those sold under the Trade Names
UCARE Polymer JR-125, UCARE Polymer JR-400 and
UCARE Polymer JR-30M.
The Stabilising agents useful in this embodiment of the
invention preferably have a weigth average molecular
weight in the range 200,000 to 800,000.
The amount of cellulose ether Stabilising agent used
depends upon a number of factors including the particle size
of the Zinc oxide, the intended use of the dispersion and the
concentration of Zinc oxide in the dispersion. Preferably, the
amount used is from 0.02 to 0.5 per cent by weight with
respect to weight of Zinc oxide. More preferably, the amount
present is from 0.1 to 0.2 per cent by weight with respect to
weight of Zinc oxide. Usually the Stabilising agent is added
to the Zinc oxide as described hereinafter after the Zinc oxide
has been coated with dense amorphous Silica.
Usually, it is necessary to Stir the cellulose ether Stabi
lising agent with water to hydrate the polymer before it is
mixed with the Zinc oxide.
In a Second embodiment of the invention, the Stabilising
agent used in the dispersion is a polyalkylene glycol. Suit
able polyalkylene glycols include polyethylene glycols or
polypropylene glycols but polyethylene glycol is preferred.
Preferably, the polyethylene glycol which is used has a
weight average molecular weight in the range 20,000 to
500,000.
The amount of polyalkylene glycol used can be varied
according to the intended end use of the Zinc oxide disper
sion but normally the amount used is from 1.5 to 7.0 per cent
by weight with respect to weight of zinc oxide. Preferably
the amount is from 2.5 to 6.0 per cent by weight with respect
to Zinc oxide.
When polyethylene glycol is used to stabilise the emul
Sion it is normally necessary to hydrate Solid polyethylene
glycol by Stirring with water and the resultant aqueous
Solution is usually then mixed with Zinc oxide particles as
described hereinafter.
The storage stability of the dispersions of the invention
which utilise a cellulose ether containing quaternary ammo
nium groups as a Stabilising agent can be improved by the
addition of a thickener to the dispersion. Suitable thickeners
include inorganic products Such as Swelling clays, for
example Laponite (Trade Mark), and organic polymerS Such
as polyalkylene glycols, especially polyethylene glycol and
cellulose ether derivatives. Preferably, the polymeric thick
enerS have a weight average molecular weight greater than
about 100,000.
The amount of thickener used is preferably in the range
1.5 to 7.0 per cent by weight with respect to weight of zinc
oxide and more preferably in the range 2.5 to 6.0 per cent by
weight with respect to Zinc oxide.
Normally, the dispersion is prepared by intensive agita
tion of the coated zinc oxide particles with water. When the
dispersion is intended for use in Sunscreens it is particularly
important that the Zinc oxide is effectively dispersed as
non-agglomerated particles. For this purpose a Suitable
means of agitation is to use a mill which employs a par
ticulate grinding medium. Such mills are bead mills
equipped with one or more agitators and using Sand, glass
beads, ceramic beads or other particles as the grinding
medium. Particularly useful are those mills which operate at
a high Speed and depending on the Size of mill a speed of the
order of 2500 rev per minute (rpm) is not unusual. For
instance mills operating at a speed of from 1000 rpm to 6000
rpm are Suitable. Agitator mills in which the tip speed of the
agitator is up to and can exceed 10 metres/sec are of use. If
desired the mill can be cooled. After the agitation by milling
has been carried out for the required time the dispersion is
Separated from the grinding medium by Screening through a
5 narrow gap. The Stabilising agent and, when used, the
thickener is preferably mixed with the zinc oxide before it is
Subjected to milling as this provides a more efficient mixing.
However, either or both of the stabilising agent or the
thickener can be mixed with the dispersion of coated Zinc
oxide after milling by any convenient means.
If desired conventional additives Such as preservatives
may also be added to the dispersion.
The dispersions according to the invention have shown
excellent Stability at high concentrations of Zinc oxide and
15 are very useful for preparing Sunscreen formulations Such as
milks, lotions, and creams and cosmetics and Veterinary
products.
The invention is illustrated by the following examples.
EXAMPLE 1.
An aqueous Slurry of Zinc oxide was prepared at a
concentration of 250 g ZnO per litre by mixing deminera
lised water, nodular Zinc oxide (average particle size 0.06
micrometre) and sodium silicate (equivalent to 2% SiO by
25
weight with respect to ZnO). The slurry was milled on a sand
mill using Ottawa Sand as a milling medium for 2 hours.
After separation of the sand the milled slurry was diluted
to 170 g ZnO per litre with demineralised water and heated
to 90° C. at which temperature it was maintained during
Subsequent deposition of dense amorphous Silica. The pH of
the slurry was adjusted to 9.4 with a solution containing 20%
by weight hydrochloric acid and addition of a solution of
Sodium silicate (equivalent to 151 g SiO2 per litre) was
35 started. During the addition of sodium silicate 20% by
weight hydrochloric acid was simultaneously added at a rate
which maintained the pH of the slurry in the range 8.5 to 9.5.
Addition was continued until the equivalent of 7.5% by
weight SiO, with respect to ZnO had been added and the
40 slurry was then stirred for 30 minutes at 90° C. Sufficient
hydrochloric acid (20% HCI by weight) to reduce the pH of
the slurry to 7.0 was then added over 30 minutes and the
slurry was then stirred for a further 30 minutes.
The product was filtered and washed by repulping until
45 the conductivity of the slurry was less than 150 uS. The zinc
oxide coated with 9.5% by weight dense amorphous silica
was spray dried (NIROFD11) by feeding a slurry containing
250 g ZnO per litre with an inlet temperature of 500 C. and
an outlet temperature of 100° C. and an atomiser disk speed
50 of 18000 rpm.
0.225 g of a quaternised cationic hydroxyethyl cellulose
sold under the Trade Name UCARE JR-125 (Union
Carbide) was added to 99.775 g demineralised water and
mixed with a propeller stirrer for 90 minutes to ensure
55 complete hydration. 1.25 g of a preservative Sold under the
Trade Name Germaben II were added to this mixture fol
lowed by 150 g of zinc oxide coated as described above. The
mixture was milled for 5 minutes in a high speed mill (Eiger
M-50-VSE) using 60 g of 1 mm glass beads as a milling
60 medium. 5.0 g of polyethylene glycol (Polyox WSR N-10)
was added to the mixture and milling was continued for a
further 15minutes. After Separation of the glass beads, a
dispersion of Zinc oxide having a Solids content of 58.5 per
cent by weight was obtained.
65 A diluted dispersion was obtained by mixing 0.02 g of the
above dispersion with 100 ml demineralised water and
extinction coefficients were obtained at a wavelength of 308
 5,914,101
S
nm (Esos), 360 nm (Esso) and 524 nm (Es2) using a
UV/visible spectrometer (Perkin Elmer Lambda 2). The
maximum extinction coefficient (E) and the wavelength % by weight
of E. (2) were also observed as follows. Phase A

1) Light mineral oil 6.5

E308 E360 Es24 Emax ^max 2) Isopropyl myristate 4.0
3) Grapeseed oil 2.5
13.7 14.5 3.3 17.3 373 4) Stearyl alcohol 1.O
5) White petroleumn jelly 1.O
1O Phase B
After Storage for 2 months no Separation or Sedimentation 6) Demineralised water 6O.7
could be detected in the dispersion and the observed extinc 7) Xanthan gum (sold under the Trade Name Keltrol RD) O.2
tion coefficients were unchanged. 8) D-Panthenol USP O.8
9) Glycerine BP 4.0
EXAMPLE 2 15 10) Sorbitan stearate (sold under the Trade Name Span 60) 6.O
11) Allantoin O.2
12) Disodium ricinoleamido MEA-sulfosuccinate (sold O.2
6.25 g of polyethylene glycol (Polyox WSR N- 10) was under the Trade Name Rewoderm S1333)
added to 100 g of demineralised water and mixed until fully 13) Dispersion of zinc oxide (58.7% ZnO by weight) 12.5
Phase C
hydrated. 150 g of Zinc oxide coated with dense amorphous
Silica as described in Example 1 was added. The mixture was 14) Mixture of alkyl parabens in phenoxyethanol (sold 0.4
milled in a high speed bead mill (Eiger M-50-VSE) with 60 under the Trade Name Phenonip)
g of 1mm glass beads as the milling medium. The dispersion
was milled for 20 minutes. The Solids content of the dis
persion after separation of the glass beads was 58.5% by Ingredient 7 was dispersed in water (ingredient 6) and
weight. 25 ingredient 9 was added. Then ingredient 13 was added with
Vigorous stirring followed by the remaining ingredients of
0.02 g of the resultant dispersion was diluted with 100 ml Phase B. This mixture was then heated to 80 C. with
demineralised water and extinction coefficients were mea constant Stirring. The ingredients of Phase A were mixed and
Sured as in Example 1. Results are given below. heated to 80° C. Phase A was then added to Phase B at 80
C. and the two phases mixed with a rotor/stator mixer for 2
minutes at 80° C. The resultant mixture was cooled with
Esos Esso Es24 Eflax ^max
stirring to 45 C. and Phase C was added. Stirring was
14.1 14.9 3.3 17.5 373 continued until the product had cooled to 30° C.
The resultant lotion had an in-vitro Sun Protection Factor
After Storage for 2 months no Separation or Sedimentation
35 (SPF) of 6.6, when measured by the method of Diffey and
could be detected in the dispersion and the observed extinc Robson, J. Soc. Cosmet. Chem., 40, 127-133, (1989).
tion coefficients were unchanged. EXAMPLE 4

EXAMPLE 3
A further Sample of the Zinc oxide dispersion used in
40 Example 3 was incorporated into a Sunscreen lotion having
A dispersion of Zinc oxide coated with dense amorphous the following formulation.
Silica was prepared as follows.
5 g of polyethylene glycol (Polyox WSR N- 10) was % by weight
added to 94.625 g of demineralised water and mixed until 45 Phase A
fully hydrated. 0.375g of a preservative sold under the Trade
Name Nipagin M Sodium (chemical name sodium methyl 1) Emulsifier (Arlacel 165 from ICI Surfactants) 5.0
4-hydroxybenzoate) were added to the mixture followed by 2) Stearyl Alcohol 1.O
3) Light mineral oil 6.O
150 g of Zinc oxide coated with dense amorphous Silica as 4) Sweet Almond oil 3.0
described in Example 1. The mixture was milled in a high 50 5) Dimethicone fluid - 350 cs (sold under the Trade 2.O
speed bead mill (Eiger M-50-VSE) with 60 g of 1 mm glass Name Dow Corning 200 Fluid)
beads as the milling medium. The dispersion was milled for 6) C-1s Alkyl Benzoate (sold under the Trade 4.5
20 minutes. The Solids content of the dispersion after Name Finsolv TN)
Phase B
separation of the glass beads was 58.7% by weight.
55 7) Demineralised water 61.4
0.02 g of the resultant dispersion was diluted with 100 ml 8) Carbopol Ultrez. 10 Polymer (from B F Goodrich Co) O.2
derineralised water and extinction coefficients were mea 9) Glycerine BP 4.0
Sured as in Example 1. Results are given below. 10) Dispersion of zinc oxide (58.7% ZnO by weight) 12.5
Phase C

60 11) Mixture of alkyl parabens in phenoxyethanol (Sold 0.4

E308 E360 Es24 Emax ^max under the Trade Name Phenonip)
13.8 14.1 3.2 16.5 373
Ingredient 8 was dispersed in the water (ingredient 7) and
The sample was found to be stable for 2 months. ingredient 9 was added followed by ingredient 10 with
65 Vigorous stirring. The ingredients of Phase A were mixed
This dispersion was incorporated into a Sunscreen lotion and Phases A and B were heated to 80° C. Phase A was
having the following formulation. added to Phase B whilst the mixture was stirred on a
 5,914,101
7 8
rotor/stator mixer. Mixing was continued until the mixture -continued
was fully homogenised. The lotion produced was cooled
with moderate stirring and Phase C was added when the % by weight
temperature reached 45 C. Stirring was continued until the Phase C
temperature reached 30° C.
8) Mixture of alkyl parabens in phenoxyethanol (sold 0.4
The lotion was tested using the method of Diffey and under the Trade Name Phenonip)
Robson and found to have an SPF of 6.5

EXAMPLE 5 The ingredients of Phase A and Phase B were separately

mixed and heated to 80 C. Phase A was added to Phase B
A further Sample of the Zinc oxide dispersion used in and mixed using a rotor/stator mixer for 2 minutes. The
Example 3 was incorporated into a Sunscreen lotion having lotion was cooled with stirring, Phase C was added at 45 C.
the following formulation. and stirring was continued until the temperature reached 30
C.
15 The lotion had an SPF of 6.0 when tested by the Diffey
% by weight and Robson method.
We claim:
Phase A 1. A Stabilised acqueous dispersion of particulate Zinc
1) Emulsifier (Arlacel 165 from ICI Surfactants) 5.0 oxide comprising water, a Stabilising agent and Zinc oxide,
2) Stearyl alcohol 1.O the particles of which are coated with dense amorphous
3) Light mineral oil 6.O Silica which has been deposited on the Surface of the Zinc
4) Sweet Almond oil 3.0 oxide particles by mixing an alkali metal Silicate and an acid
5) Dimethicone fluid - 350 cs (sold under the Trade 2.0 in the presence of Zinc oxide particles in an aqueous
Name Dow Corning 200 Fluid) Suspension, the aqueous Suspension being maintained at a
6) C-1s Alkyl Benzoate (sold under the Trade Name 4.5 pH of at least 8 during the mixing of Said Silicate and Said
Finsolv TN) 25
acid.
Phase B
2. A Stabilised aqueous dispersion according to claim 1 in
7) Demineralised water 53.9 which the particles of uncoated Zinc oxide have an average
8) Xanthan gum (sold under the Trade Name Keltrol RD) O.2 primary particle size in the range 0.005 to 0.20 micrometre.
9) Glycerine BP 4.0 3. A Stabilised acqueous dispersion according to claim 1
10) Dispersion of zinc oxide (58.7% ZnO by weight) 2O.O
Phase C which contains at least 40 per cent Zinc oxide by weight.
4. A Stabilised acqueous dispersion according to claim 1
11) Mixture of alkyl parabens in phenoxyethanol (sold 0.4 which contains not more than 75 per cent Zinc oxide by
under the Trade Name Phenonip) Weight.
5. A Stabilised aqueous dispersion according to claim 2 in
Ingredient 8 was dispersed in water (ingredient 7) and
35 which the Zinc oxide particles are coated with dense amor
phous Silica in an amount between 5 and 20 per cent by
ingredient 9 was added. Then ingredient 10 was added with weight calculated as SiO2 with respect to Zinc oxide.
vigorous stirring. This mixture was then heated to 80° C. 6. A Stabilised aqueous dispersion according to claim 1 in
with constant Stirring. The ingredients of Phase A were which the Zinc oxide particles are coated with a hydrous
mixed and heated to 80 C. Phase A was then added to Phase 40 oxide in addition to the coating of dense amorphous Silica
B at 80 C. and the two phases mixed with a rotor/stator Said hydrous oxide being a hydrous oxide of a metal Selected
mixer for 3 minutes at 80° C. The resultant mixture was from the group consisting of aluminium, Zirconium and
cooled with stirring to 45 C. and Phase C was added. titanium.
Stirring was continued until the product had cooled to 30° C. 7. A Stabilised aqueous dispersion according to claim 1 in
The resultant lotion, when tested by the Diffey and 45 which the Stabilising agent is a cellulose ether which con
Robson method, had an SPF of 12.5. tains quaternary ammonium groups.
8. A Stabilised aqueous dispersion according to claim 7 in
EXAMPLE 6 which the Stabilising agent is a polymer having a backbone
of anhydroglucose units with pendant Substituent groups
A further Sample of the dispersion of Zinc oxide used in 50 containing quaternary ammonium functionality Spaced
Example 3 was incorporated into a Sunscreen lotion having along the backbone.
the following formulation. 9. A Stabilised aqueous dispersion according to claim 8 in
which ether groups which do not contain a quaternary
ammonium radical are present in the polymer molecule.
% by weight 55 10. A Stabilised aqueous dispersion according to claim 7
Phase A in which the Stabilising agent is the reaction product of a
quaternary ammonium chloride of hydroxyethyl cellulose
1) Light mineral oil 4.0 and a trimethyl ammonium Substituted epoxide.
2) Octyl palmitate 6.O 11. A Stabilised aqueous dispersion according to claim 7
3) Cetylfstearyl alcohol 1.O 60 in which the Stabilising agent has a weight average molecu
4) Emulsifying mixture (Hydrolactol 70 from Gattefosse 16.0
SA) lar weight in the range 200,000 to 800,000.
5) Dimethicone fluid (sold under the Trade Name 3.0 12. A Stabilised aqueous dispersion according to claim 7
Dow Corning 593 Fluid) in which the Stabilising agent is present in an amount in the
Phase B
range 0.02 to 0.5 per cent by weight with respect to weight
6) Demineralised water 57.1 65 of Zinc oxide.
7) Dispersion of zinc oxide (58.7% ZnO by weight) 12.5 13. A Stabilised aqueous dispersion according to claim 7
which contains a thickener Selected from the group consist
 5,914,101
9 10
ing of Swelling clays, polyalkylene glycols and cellulose
ether derivatives.
14. A Stabilised acqueous dispersion according to claim 13
in which the thickener is a polymer having a molecular
weight greater than 100,000.
15. A Stabilised acqueous dispersion according to claim 13
in which the thickener is present in an amount in the range
1.5 to 7.0 per cent by weight with respect to weight of zinc
oxide.
16. A Stabilised aqueous dispersion according to claim 1
in which the Stabilising agent is a polyalkylene glycol.
17. A Stabilised acqueous dispersion according to claim 16
in which the Stabilising agent is a polyethylene glycol
having a weight average molecular weight in the range
20,000 to 500,000.
18. A Stabilised acqueous dispersion according to claim 16
in which the polyalkylene glycol is present in an amount in
the range 1.5 to 7.0 per cent by weight with respect to weight
of Zinc oxide.
19. A method for the preparation of a stabilised aqueous
dispersion comprising mixing water, a Stabilising agent and
Zinc oxide the particles of which are coated with dense
amorphous Silica which has been deposited on the Zinc oxide
particles by mixing an alkali metal Silicate and an acid in the
presence of Zinc oxide particles in an aqueous Suspension,
the aqueous Suspension being maintained at a pH of at least
8 during mixing of Said Silicate and Said acid.
20. A method according to claim 19 in which the acid is
Selected from the group consisting of hydrochloric acid and
Sulphuric acid.
21. A method according to claim 19 in which a solution
of an alkali metal Silicate and an alkaline Suspension of Zinc
oxide particles are mixed and the resulting mixture is slowly
acidified.
22. A method according to claim 19 in which an alkaline
Solution of an alkali metal Silicate and a mineral acid are
Simultaneously added to a Suspension of Zinc oxide
particles, the Suspension being maintained at a pH of at least
8 during addition of the Silicate and the acid.
23. A method according to claim 19 in which the Suspen
Sion of Zinc oxide particles is maintained at a temperature in
the range 60° C. to 100° C. during deposition of the dense
amorphous Silica.
24. A method according to claim 19 in which a dispersing
15
agent Selected from the group consisting of Sodium Silicate
and potassium Silicate is present in the Zinc oxide dispersion
during deposition of dense amorphous Silica.
25. A method according to claim 24 in which the dispers
ing agent is present in an amount in the range 1.0 to 5.0 per
cent by weight expressed as SiO2 with respect to Zinc oxide.
26. A method according to claim 19 in which the coated
particles of Zinc oxide are mixed with water in a bead mill
which employs a grinding medium Selected from the group
consisting of Sand, glass beads and ceramic beads.
25 27. A method according to claim 26 in which the mill is
operated at a speed of 1000 rpm to 6000 rpm.
28. A method according to claim 26 in which the stabi
lising agent and, when used, a thickener are mixed with the
Zinc oxide before milling.
k k k k k